Exhaust purification system of internal combustion engine

ABSTRACT

A method for purifying exhaust gas of an internal combustion engine including flowing an exhaust gas containing NO x  and a concentration of hydrocarbons in an exhaust gas passage that contains an exhaust purification catalyst, wherein the concentration of hydrocarbons is vibrated within a predetermined range of amplitude and period, and a least a portion of the hydrocarbons are reformed by the exhaust purification catalyst; reacting the NO x  contained in the exhaust gas and the reformed hydrocarbons to produce a reducing intermediate; and chemically reducing, wherein at the time of engine operation, a demanded produced amount of the reducing intermediate required for chemically reducing the NO x  is calculated, and the amplitude and vibration period of the concentration of hydrocarbons flowing into the exhaust purification catalyst are controlled so that an amount of the reducing intermediate produced becomes the demanded produced amount.

This is a Division of application Ser. No. 13/202,694 filed Sep. 20,2011, which in turn is a National Stage application ofPCT/JP2010/065186, filed on Aug. 30, 2010. The disclosure of the priorapplications is hereby incorporated by reference herein in its entirety.

TECHNICAL FIELD

The present invention relates to an exhaust purification system of aninternal combustion engine.

BACKGROUND ART

Known in the art is an internal combustion engine which arranges, in anengine exhaust passage, an NO_(x) storage catalyst which stores NO_(x)which is contained in exhaust gas when the air-fuel ratio of theinflowing exhaust gas is lean and which releases the stored NO_(x) whenthe air-fuel ratio of the inflowing exhaust gas becomes rich, whicharranges, in the engine exhaust passage upstream of the NO_(x) storagecatalyst, an oxidation catalyst which has an adsorption function, andwhich feeds hydrocarbons into the engine exhaust passage upstream of theoxidation catalyst to make the air-fuel ratio of the exhaust gas flowinginto the NO_(x) storage catalyst rich when released NO_(x) from theNO_(x) storage catalyst (for example, see Patent Literature 1).

In this internal combustion engine, the hydrocarbons which are fed whenreleased NO_(x) from the NO_(x) storage catalyst are made gaseoushydrocarbons at the oxidation catalyst, and the gaseous hydrocarbons arefed to the NO_(x) storage catalyst. As a result, the NO_(x) which isreleased from the NO_(x) storage catalyst is reduced well.

CITATION LIST Patent Literature

-   Patent Literature 1: Japanese Patent No. 3969450

SUMMARY OF INVENTION Technical Problem

However, there is the problem that when the NO_(x) storage catalystbecomes a high temperature, the NO_(x) purification rate falls.

An object of the present invention is to provide an exhaust purificationsystem of an internal combustion engine which can obtain a high NO_(x)purification rate even if the temperature of the exhaust purificationcatalyst becomes a high temperature.

Solution to Problem

According to the present invention, there is provided an exhaustpurification system of an internal combustion engine wherein an exhaustpurification catalyst is arranged in an engine exhaust passage forreacting NO_(x) contained in exhaust gas and reformed hydrocarbons toproduce a reducing intermediate containing nitrogen and hydrocarbons, aprecious metal catalyst is carried on an exhaust gas flow surface of theexhaust purification catalyst and a basic exhaust gas flow surface partis formed around the precious metal catalyst, the exhaust purificationcatalyst has a property of producing a reducing intermediate andreducing the NO_(x) contained in the exhaust gas by a reducing action ofthe produced reducing intermediate if causing vibration of aconcentration of hydrocarbons flowing into the exhaust purificationcatalyst by within a predetermined range of amplitude and within apredetermined range of period and has a property of being increased instorage amount of NO_(x) which is contained in the exhaust gas iflengthening the vibration period of the hydrocarbon concentration morethan the predetermined range, and, at the time of engine operation, ademanded produced amount of the reducing intermediate required forreducing the NO_(x) is calculated and the amplitude and vibration periodof the concentration of hydrocarbons flowing into the exhaustpurification catalyst are controlled so that an amount of production ofthe reducing intermediate becomes the demanded produced amount.

Advantageous Effects of Invention

Even if the temperature of the exhaust purification catalyst becomes ahigh temperature, a high NO_(x) purification rate can be obtained.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is an overall view of a compression ignition type internalcombustion engine.

FIG. 2 is a view schematically showing a surface part of a catalystcarrier.

FIG. 3 is a view for explaining an oxidation reaction in an exhaustpurification catalyst.

FIG. 4 is a view showing a change of an air-fuel ratio of exhaust gasflowing into an exhaust purification catalyst.

FIG. 5 is a view showing an NO_(x) purification rate.

FIGS. 6A and 6B are views for explaining an oxidation reduction reactionin an exhaust purification catalyst.

FIGS. 7A and 7B are views for explaining an oxidation reduction reactionin an exhaust purification catalyst.

FIG. 8 is a view showing a change of an air-fuel ratio of exhaust gasflowing into an exhaust purification catalyst.

FIG. 9 is a view of an NO_(x) purification rate.

FIG. 10 is a time chart showing a change of an air-fuel ratio of exhaustgas flowing into an exhaust purification catalyst.

FIG. 11 is a time chart showing a change of an air-fuel ratio of exhaustgas flowing into an exhaust purification catalyst.

FIG. 12 is a view showing a relationship between an oxidizing strengthof an exhaust purification catalyst and a demanded minimum air-fuelratio X.

FIG. 13 is a view showing a relationship between an oxygen concentrationin exhaust gas and an amplitude ΔH of a hydrocarbon concentration givingthe same NO_(x) purification rate.

FIG. 14 is a view showing a relationship between an amplitude ΔH of ahydrocarbon concentration and an NO_(x) purification rate.

FIG. 15 is a view showing a relationship of a vibration period ΔT of ahydrocarbon concentration and an NO_(x) purification rate.

FIG. 16 is a time chart showing changes in an air-fuel ratio of exhaustgas flowing into an exhaust purification catalyst.

FIG. 17 is a view showing a map of a stored NO_(x) amount NOXA.

FIG. 18 is a view showing an NO_(x) discharge rate NOXB.

FIG. 19 is a view showing a fuel injection timing.

FIG. 20 is a view showing a map of additional fuel WR.

FIGS. 21A, 21B, and 21C are views showing an NO_(x) release rate.

FIGS. 22A and 22B are views showing a reducing intermediate holding timeetc.

FIGS. 23A and 23B are views showing reducing intermediate productionrates K₁ and K₂.

FIGS. 24A and 24B are views showing a maximum produced amount M of areducing intermediate.

FIGS. 25A and 25B views showing a map of the fuel feed amount W etc.

FIG. 26 is a view showing an NO_(x) purification rate and an NO_(x)storage rate.

FIG. 27 is a time chart showing changes in the air-fuel ratio (A/F)in ofthe exhaust gas etc. at the time of switching from a second NO_(x)purification method to a first NO_(x) purification method.

FIG. 28 is a flow chart for NO_(x) purification control.

FIGS. 29A and 29B are views showing a change of the air-fuel ratio ofthe exhaust gas flowing into the exhaust purification catalyst.

FIG. 30 is a view showing a map of the opening degree θB of the throttlevalve.

FIG. 31 is a time chart showing changes in the air-fuel ratio (A/F)in ofthe exhaust gas etc. at the time of switching from a second NO_(x)purification method to a first NO_(x) purification method.

FIG. 32 is a flow chart for NO_(x) purification control.

FIG. 33 is a view of a time chart at the time of rich control.

FIGS. 34A and 34B are views showing correction coefficients.

DESCRIPTION OF EMBODIMENTS

FIG. 1 is an overall view of a compression ignition type internalcombustion engine.

Referring to FIG. 1, 1 indicates an engine body, 2 a combustion chamberof each cylinder, 3 an electronically controlled fuel injector forinjecting fuel into each combustion chamber 2, 4 an intake manifold, and5 an exhaust manifold. The intake manifold 4 is connected through anintake duct 6 to an outlet of a compressor 7 a of an exhaustturbocharger 7, while an inlet of the compressor 7 a is connectedthrough an intake air amount detector 8 to an air cleaner 9. Inside theintake duct 6, a throttle valve 10 driven by a step motor is arranged.Furthermore, around the intake duct 6, a cooling device 11 is arrangedfor cooling the intake air which flows through the inside of the intakeduct 6. In the embodiment shown in FIG. 1, the engine cooling water isguided to the inside of the cooling device 11 where the engine coolingwater is used to cool the intake air.

On the other hand, the exhaust manifold 5 is connected to an inlet of anexhaust turbine 7 b of the exhaust turbocharger 7. The outlet of theexhaust turbine 7 b is connected through an exhaust pipe 12 to an inletof the exhaust purification catalyst 13, while the outlet of the exhaustpurification catalyst 13 is connected to a particulate filter 14 fortrapping particulate which is contained in the exhaust gas. Inside theexhaust pipe 12 upstream of the exhaust purification catalyst 13, ahydrocarbon feed valve 15 is arranged for feeding hydrocarbons comprisedof diesel oil or other fuel used as fuel for a compression ignition typeinternal combustion engine. In the embodiment shown in FIG. 1, dieseloil is used as the hydrocarbons which are fed from the hydrocarbon feedvalve 15. Note that, the present invention can also be applied to aspark ignition type internal combustion engine in which fuel is burnedunder a lean air-fuel ratio. In this case, from the hydrocarbon feedvalve 15, hydrocarbons comprised of gasoline or other fuel used as fuelof a spark ignition type internal combustion engine are fed.

On the other hand, the exhaust manifold 5 and the intake manifold 4 areconnected with each other through an exhaust gas recirculation(hereinafter referred to as an “EGR”) passage 16. Inside the EGR passage16, a electronically controlled EGR control valve 17 is arranged.Further, around the EGR passage 16, a cooling device 18 is arranged forcooling EGR gas flowing through the inside of the EGR passage 16. In theembodiment shown in FIG. 1, the engine cooling water is guided to theinside of the cooling device 18 where the engine cooling water is usedto cool the EGR gas. On the other hand, each fuel injector 3 isconnected through a fuel feed tube 19 to a common rail 20. This commonrail 20 is connected through an electronically controlled variabledischarge fuel pump 21 to a fuel tank 22. The fuel which is storedinside of the fuel tank 22 is fed by the fuel pump 21 to the inside ofthe common rail 20. The fuel which is fed to the inside of the commonrail 20 is fed through each fuel feed tube 19 to the fuel injector 3.

An electronic control unit 30 is comprised of a digital computerprovided with a ROM (read only memory) 32, a RAM (random access memory)33, a CPU (microprocessor) 34, an input port 35, and an output port 36,which are connected with each other by a bidirectional bus 31.Downstream of the exhaust purification catalyst 13, a temperature sensor23 is attached for detecting the temperature of the exhaust purificationcatalyst 13. The particulate filter 14 has a differential pressuresensor 24 attached for detecting the differential pressure before andafter the particulate filter 14. Further, at the collecting portion ofthe exhaust manifold 5, an air-fuel ratio sensor 25 is arranged. Theoutput signals of these temperature sensor 23, differential pressuresensor 24, air-fuel ratio sensor 25, and intake air amount detector 8are input through corresponding AD converters 37 to the input port 35.Further, an accelerator pedal 40 has a load sensor 41 connected to itwhich generates an output voltage proportional to the amount ofdepression L of the accelerator pedal 40. The output voltage of the loadsensor 41 is input through a corresponding AD converter 37 to the inputport 35. Furthermore, at the input port 35, a crank angle sensor 42 isconnected which generates an output pulse every time a crankshaftrotates by, for example, 15°. On the other hand, the output port 36 isconnected through corresponding drive circuits 38 to each fuel injector3, a step motor for driving the throttle valve 10, the hydrocarbon feedvalve 15, the EGR control valve 17, and the fuel pump 21.

FIG. 2 schematically shows a surface part of a catalyst carrier which iscarried on a substrate of the exhaust purification catalyst 13. At thisexhaust purification catalyst 13, as shown in FIG. 2, for example, thereis provided a catalyst carrier 50 made of alumina on which preciousmetal catalysts 51 and 52 are carried. Furthermore, on this catalystcarrier 50, a basic layer 53 is formed which includes at least oneelement selected from potassium K, sodium Na, cesium Cs, or another suchalkali metal, barium Ba, calcium Ca, or another such alkali earth metal,a lanthanoid or another such rare earth and silver Ag, copper Cu, ironFe, iridium Ir, or another metal able to donate electrons to NO_(x). Theexhaust gas flows along the top of the catalyst carrier 50, so theprecious metal catalysts 51 and 52 can be said to be carried on theexhaust gas flow surface of the exhaust purification catalyst 13.Further, the surface of the basic layer 53 exhibits basicity, so thesurface of the basic layer 53 is called the basic exhaust gas flowsurface part 54.

On the other hand, in FIG. 2, the precious metal catalyst 51 iscomprised of platinum Pt, while the precious metal catalyst 52 iscomprised of rhodium Rh. That is, the precious metal catalysts 51 and 52which are carried on the catalyst carrier 50 are comprised of platinumPt and rhodium Rh. Note that, on the catalyst carrier 50 of the exhaustpurification catalyst 13, in addition to platinum Pt and rhodium Rh,palladium Pd may be further carried or, instead of rhodium Rh, palladiumPd may be carried. That is, the precious metal catalysts 51 and 52 whichare carried on the catalyst carrier 50 are comprised of platinum Pt andat least one of rhodium Rh and palladium Pd.

If hydrocarbons are injected from the hydrocarbon feed valve 15 into theexhaust gas, the hydrocarbons are reformed by the exhaust purificationcatalyst 13. In the present invention, at this time, the reformedhydrocarbons are used to remove the NO_(x) at the exhaust purificationcatalyst 13. FIG. 3 schematically shows the reforming action performedat the exhaust purification catalyst 13 at this time. As shown in FIG.3, the hydrocarbons HC which are injected from the hydrocarbon feedvalve 15 become radical hydrocarbons HC with a small carbon number bythe catalyst 51.

Note that, even if injecting fuel, that is, hydrocarbons, from the fuelinjector 3 into the combustion chamber 2 during the latter half of theexpansion stroke or during the exhaust stroke, the hydrocarbons arereformed inside of the combustion chamber 2 or at the exhaustpurification catalyst 13, and the NO_(x) which is contained in theexhaust gas is removed by the reformed hydrocarbons at the exhaustpurification catalyst 13. Therefore, in the present invention, insteadof feeding hydrocarbons from the hydrocarbon feed valve 15 to the insideof the engine exhaust passage, it is also possible to feed hydrocarbonsinto the combustion chamber 2 during the latter half of the expansionstroke or during the exhaust stroke. In this way, in the presentinvention, it is also possible to feed hydrocarbons to the inside of thecombustion chamber 2, but below the present invention is explainedtaking as an example the case of injecting hydrocarbons from thehydrocarbon feed valve 15 to the inside of the engine exhaust passage.

FIG. 4 shows the timing of feeding hydrocarbons from the hydrocarbonfeed valve 15 and the changes in the air-fuel ratio (A/F)in of theexhaust gas flowing into the exhaust purification catalyst 13. Notethat, the changes in the air-fuel ratio (A/F)in depend on the change inconcentration of the hydrocarbons in the exhaust gas which flows intothe exhaust purification catalyst 13, so it can be said that the changein the air-fuel ratio (A/F)in shown in FIG. 4 expresses the change inconcentration of the hydrocarbons. However, if the hydrocarbonconcentration becomes higher, the air-fuel ratio (A/F)in becomessmaller, so, in FIG. 4, the more the rich side the air-fuel ratio(A/F)in becomes, the higher the hydrocarbon concentration.

FIG. 5 shows the NO_(x) purification rate by the exhaust purificationcatalyst 13 with respect to the catalyst temperatures of the exhaustpurification catalyst 13 when periodically making the concentration ofhydrocarbons flowing into the exhaust purification catalyst 13 change soas to, as shown in FIG. 4, make the air-fuel ratio (A/F)in of theexhaust gas flowing to the exhaust purification catalyst 13 change. Theinventors engaged in research relating to NO_(x) purification for a longtime. In the process of research, they learned that if making theconcentration of hydrocarbons flowing into the exhaust purificationcatalyst 13 vibrate by within a predetermined range of amplitude andwithin a predetermined range of period, as shown in FIG. 5, an extremelyhigh NO_(x) purification rate is obtained even in a 400° C. or higherhigh temperature region.

Furthermore, at this time, a large amount of reducing intermediatecontaining nitrogen and hydrocarbons continues to be held or adsorbed onthe surface of the basic layer 53, that is, on the basic exhaust gasflow surface part 54 of the exhaust purification catalyst 13. It islearned that this reducing intermediate plays a central role inobtaining a high NO_(x) purification rate. Next, this will be explainedwith reference to FIGS. 6A and 6B. Note that, these FIGS. 6A and 6Bschematically show the surface part of the catalyst carrier 50 of theexhaust purification catalyst 13. These FIGS. 6A and 6B show thereaction which is presumed to occur when the concentration ofhydrocarbons flowing into the exhaust purification catalyst 13 is madeto vibrate by within a predetermined range of amplitude and within apredetermined range of period.

FIG. 6A shows when the concentration of hydrocarbons flowing into theexhaust purification catalyst 13 is low, while FIG. 6B shows whenhydrocarbons are fed from the hydrocarbon feed valve 15 and theconcentration of hydrocarbons flowing into the exhaust purificationcatalyst 13 becomes high.

Now, as will be understood from FIG. 4, the air-fuel ratio of theexhaust gas which flows into the exhaust purification catalyst 13 ismaintained lean except for an instant, so the exhaust gas which flowsinto the exhaust purification catalyst 13 normally becomes a state ofoxygen excess. Therefore, the NO which is contained in the exhaust gas,as shown in FIG. 6A, is oxidized on the platinum 51 and becomes NO₂.Next, this NO₂ is supplied with electrons from the platinum 51 andbecomes NO₂ ⁻. Therefore, a large amount of NO₂ ⁻ is produced on theplatinum 51. This NO₂ ⁻ is strong in activity. Above, this NO₂ ⁻ iscalled the active NO₂*.

On the other hand, if hydrocarbons are fed from the hydrocarbon feedvalve 15, as shown in FIG. 3, the hydrocarbons are reformed and becomeradicalized inside of the exhaust purification catalyst 13. As a result,as shown in FIG. 6B, the hydrocarbon concentration around the activeNO₂* becomes higher. In this regard, after the active NO₂* is produced,if the state of a high oxygen concentration around the active NO₂*continues for a predetermined time or more, the active NO₂* is oxidizedand is absorbed in the basic layer 53 in the form of nitrate ions NO₃ ⁻.However, if the hydrocarbon concentration around the active NO₂* is madehigher before this predetermined time passes, as shown in FIG. 6B, theactive NO₂ reacts on the platinum 51 with the radical hydrocarbons HCwhereby a reducing intermediate is produced. This reducing intermediateis adhered or adsorbed on the surface of the basic layer 53.

Note that, at this time, the first produced reducing intermediate isconsidered to be a nitro compound R—NO₂. If this nitro compound R—NO₂ isproduced, the result becomes a nitrile compound R—CN, but this nitrilecompound R—CN can only survive for an instant in this state, soimmediately becomes an isocyanate compound R—NCO. This isocyanatecompound R—NCO, when hydrolyzed, becomes an amine compound R—NH₂.However, in this case, what is hydrolyzed is considered to be part ofthe isocyanate compound R—NCO. Therefore, as shown in FIG. 6B, themajority of the reducing intermediate which is held or adsorbed on thesurface of the basic layer 53 is believed to be the isocyanate compoundR—NCO and amine compound R—NH₂.

On the other hand, as shown in FIG. 6B, if the produced reducingintermediate is surrounded by the hydrocarbons HC, the reducingintermediate is blocked by the hydrocarbons HC and the reaction will notproceed any further. In this case, if the concentration of hydrocarbonsflowing into the exhaust purification catalyst 13 is lowered and therebythe oxygen concentration becomes higher, the hydrocarbons around thereducing intermediate will be oxidized. As a result, as shown in FIG.6A, the reducing intermediate and the active NO₂* will react. At thistime, the active NO₂* reacts with the reducing intermediate R—NCO orR—NH₂ to form N₂, CO₂, and H₂O and consequently the NO_(x) is removed.

In this way, in the exhaust purification catalyst 13, by making theconcentration of hydrocarbons flowing into the exhaust purificationcatalyst 13 higher, a reducing intermediate is produced. By making theconcentration of hydrocarbons flowing into the exhaust purificationcatalyst 13 lower and raising the oxygen concentration, the active NO₂*reacts with the reducing intermediate and the NO_(x) is removed. Thatis, in order for the exhaust purification catalyst 13 to remove theNO_(x), the concentration of hydrocarbons flowing into the exhaustpurification catalyst 13 has to be periodically changed.

Of course, in this case, it is necessary to raise the concentration ofhydrocarbons to a concentration sufficiently high for producing thereducing intermediate and it is necessary to lower the concentration ofhydrocarbons to a concentration sufficiently low for making the producedreducing intermediate react with the active NO₂*. That is, it isnecessary to make the concentration of hydrocarbons flowing into theexhaust purification catalyst 13 vibrate by within a predetermined rangeof amplitude. Note that, in this case, it is necessary to hold asufficient amount of reducing intermediate R—NCO or R—NH₂ on the basiclayer 53, that is, the basic exhaust gas flow surface part 24, until theproduced reducing intermediate reacts with the active NO₂*. For thisreason, the basic exhaust gas flow surface part 24 is provided.

On the other hand, if lengthening the feed period of the hydrocarbons,the time in which the oxygen concentration becomes higher becomes longerin the period after the hydrocarbons are fed until the hydrocarbons arenext fed. Therefore, the active NO₂* is absorbed in the basic layer 53in the form of nitrates without producing a reducing intermediate. Toavoid this, it is necessary to make the concentration of hydrocarbonsflowing into the exhaust purification catalyst 13 vibrate by within apredetermined range of period.

Therefore, in an embodiment of the present invention, to make the NO_(x)contained in the exhaust gas and the reformed hydrocarbons react andproduce the reducing intermediate R—NCO or R—NH₂ containing nitrogen andhydrocarbons, precious metal catalysts 51 and 52 are carried on theexhaust gas flow surface of the exhaust purification catalyst 13. Tohold the produced reducing intermediate R—NCO or R—NH₂ inside theexhaust purification catalyst 13, a basic exhaust gas flow surface part54 is formed around the precious metal catalysts 51 and 52. Due to thereducing action of the reducing intermediate R—NCO or R—NH₂ which isheld on the basic exhaust gas flow surface part 54, the NO_(x) isreduced. The vibration period of the hydrocarbon concentration is madethe vibration period required for continuation of the production of thereducing intermediate R—NCO or R—NH₂. Incidentally, in the example shownin FIG. 4, the injection interval is made 3 seconds.

If the vibration period of the hydrocarbon concentration, that is, thefeed period of the hydrocarbons HC, is made longer than the abovepredetermined range of period, the reducing intermediate R—NCO or R—NHdisappears from the surface of the basic layer 53. At this time, theactive NO₂* which is produced on the platinum Pt 53, as shown in FIG.7A, diffuses in the basic layer 53 in the form of nitrate ions NO₃ ⁻ andbecomes nitrates. That is, at this time, the NO_(x) in the exhaust gasis absorbed in the form of nitrates inside of the basic layer 53.

On the other hand, FIG. 7B shows the case where the air-fuel ratio ofthe exhaust gas which flows into the exhaust purification catalyst 13 ismade the stoichiometric air-fuel ratio or rich when the NO_(x) isabsorbed in the form of nitrates inside of the basic layer 53. In thiscase, the oxygen concentration in the exhaust gas falls, so the reactionproceeds in the opposite direction (NO₃ ⁻→NO₂) and consequently thenitrates absorbed in the basic layer 53 become nitrate ions NO₃ ⁻ one byone and, as shown in FIG. 7B, are released from the basic layer 53 inthe form of NO₂. Next, the released NO₂ is reduced by the hydrocarbonsHC and CO contained in the exhaust gas.

FIG. 8 shows the case of making the air-fuel ratio (A/F)in of theexhaust gas which flows into the exhaust purification catalyst 13temporarily rich slightly before the NO_(x) absorption ability of thebasic layer 53 becomes saturated. Note that, in the example shown inFIG. 8, the time interval of this rich control is 1 minute or more. Inthis case, the NO_(x) which was absorbed in the basic layer 53 when theair-fuel ratio (A/F)in of the exhaust gas was lean is released all atonce from the basic layer 53 and reduced when the air-fuel ratio (A/F)inof the exhaust gas is made temporarily rich. Therefore, in this case,the basic layer 53 plays the role of an absorbent for temporarilyabsorbing NO_(x).

Note that, at this time, sometimes the basic layer 53 temporarilyadsorbs the NO_(x) Therefore, if using term of storage as a termincluding both absorption and adsorption, at this time, the basic layer53 performs the role of an NO_(x) storage agent for temporarily storingthe NO_(x). That is, in this case, if the ratio of the air and fuel(hydrocarbons) which are fed into the engine intake passage, combustionchambers 2, and exhaust passage upstream of the exhaust purificationcatalyst 13 is called the air-fuel ratio of the exhaust gas, the exhaustpurification catalyst 13 functions as an NO_(x) storage catalyst whichstores the NO_(x) when the air-fuel ratio of the exhaust gas is lean andreleases the stored NO_(x) when the oxygen concentration in the exhaustgas falls.

FIG. 9 shows the NO_(x) purification rate when making the exhaustpurification catalyst 13 function as an NO_(x) storage catalyst in thisway. Note that, the abscissa of the FIG. 9 shows the catalysttemperature TC of the exhaust purification catalyst 13. When making theexhaust purification catalyst 13 function as an NO_(x) storage catalyst,as shown in FIG. 9, when the catalyst temperature TC is 300° C. to 400°C., an extremely high NO_(x) purification rate is obtained, but when thecatalyst temperature TC becomes a 400° C. or higher high temperature,the NO_(x) purification rate falls.

In this way, when the catalyst temperature TC becomes 400° C. or more,the NO_(x) purification rate falls because if the catalyst temperatureTC becomes 400° C. or more, the nitrates break down by heat and arereleased in the form of NO₂ from the exhaust purification catalyst 13.That is, so long as storing NO_(x) in the form of nitrates, when thecatalyst temperature TC is high, it is difficult to obtain a high NO_(x)purification rate. However, in the new NO_(x) purification method shownfrom FIG. 4 to FIGS. 6A and 6B, as will be understood from FIGS. 6A and6B, nitrates are not formed or even if formed are extremely fine inamount, consequently, as shown in FIG. 5, even when the catalysttemperature TC is high, a high NO_(x) purification rate is obtained.

Therefore, in the present invention, an exhaust purification catalyst 13is arranged in the engine exhaust passage for making the NO_(x)contained in the exhaust gas and the reformed hydrocarbon react.Precious metal catalysts 51 and 52 are carried on the exhaust gas flowsurface of the exhaust purification catalyst 13. Around the preciousmetal catalysts 51 and 52, a basic exhaust gas flow surface part 54 isformed. The exhaust purification catalyst 13 has the property ofreducing the NO_(x) which is contained in the exhaust gas if making theconcentration of hydrocarbons flowing into the exhaust purificationcatalyst 13 vibrate by within a predetermined range of amplitude andwithin a predetermined range of period and has the property of thestorage amount of the NO_(x) which is contained in the exhaust gasincreasing if making the vibration period of the hydrocarbonconcentration longer than this predetermined range. At the time ofengine operation, the amplitude and the vibration period of theconcentration of hydrocarbons flowing into the exhaust purificationcatalyst 13 are controlled so as to enable the production of asufficient amount of reducing intermediate for reducing the NO_(x). Dueto this, the NO_(x) which is contained in the exhaust gas is reduced inthe exhaust purification catalyst 13.

That is, the NO_(x) purification method which is shown from FIG. 4 toFIGS. 6A and 6B can be said to be a new NO_(x) purification methoddesigned to remove NO_(x) without forming almost any nitrates in thecase of using an exhaust purification catalyst which carries a preciousmetal catalyst and forms a basic layer which can absorb NO_(x). Inactuality, when using this new NO_(x) purification method, the nitrateswhich are detected from the basic layer 53 become much smaller in amountcompared with the case where making the exhaust purification catalyst 13function as an NO_(x) storage catalyst. Note that this new NO_(x)purification method will be called the first NO_(x) purification methodbelow.

Next, referring to FIG. 10 to FIG. 15, the first NO_(x) purificationmethod will be explained in a bit more detail.

FIG. 10 shows enlarged the change in the air-fuel ratio (A/F)in shown inFIG. 4. Note that, as explained above, the change in the air-fuel ratio(A/F)in of the exhaust gas flowing into this exhaust purificationcatalyst 13 simultaneously shows the change in concentration of thehydrocarbons which flow into the exhaust purification catalyst 13. Notethat, in FIG. 10, ΔH shows the amplitude of the change in concentrationof hydrocarbons HC which flow into the exhaust purification catalyst 13,while ΔT shows the vibration period of the concentration of thehydrocarbons which flow into the exhaust purification catalyst 13.

Furthermore, in FIG. 10, (A/F)b shows the base air-fuel ratio whichshows the air-fuel ratio of the combustion gas for generating the engineoutput. In other words, this base air-fuel ratio (A/F)b shows theair-fuel ratio of the exhaust gas which flows into the exhaustpurification catalyst 13 when stopping the feed of hydrocarbons. On theother hand, in FIG. 10, X shows the upper limit of the air-fuel ratio(A/F)in which is used for producing the reducing intermediate withoutthe produced active NO₂* being stored in the form of nitrates inside thebasic layer 53. To make the active NO₂* and the reformed hydrocarbonsreact and produce the reducing intermediate, it is necessary to make theair-fuel ratio (A/F)in lower than the upper limit X of this air-fuelratio.

In other words, in FIG. 10, X shows the lower limit of the concentrationof hydrocarbons required for making the active NO_(x)* and reformedhydrocarbon react to produce a reducing intermediate. To produce thereducing intermediate, the concentration of hydrocarbons has to be madehigher than this lower limit X. In this case, whether the reducingintermediate is produced is determined by the ratio of the oxygenconcentration and hydrocarbon concentration around the active NO₂*, thatis, the air-fuel ratio (A/F)in. The upper limit X of the air-fuel ratiorequired for producing the reducing intermediate will below be calledthe demanded minimum air-fuel ratio.

In the example shown in FIG. 10, the demanded minimum air-fuel ratio Xbecomes rich. Therefore, in this case, to produce the reducingintermediate, the air-fuel ratio (A/F)in is instantaneously made thedemanded minimum air-fuel ratio X or less, that is, is made rich. Asopposed to this, in the example shown in FIG. 11, the demanded minimumair-fuel ratio X becomes lean. In this case, the reducing intermediateis produced by maintaining the air-fuel ratio (A/F)in lean andperiodically making the air-fuel ratio (A/F)in fall.

In this case, whether the demanded minimum air-fuel ratio X becomes richor becomes lean depends on the oxidizing strength of the exhaustpurification catalyst 13. In this case, the exhaust purificationcatalyst 13, for example, becomes stronger in oxidizing strength ifincreasing the carried amount of the precious metal 51 and becomesstronger in oxidizing strength if strengthening the acidity. Therefore,the oxidizing strength of the exhaust purification catalyst 13 changesdue to the carried amount of the precious metal 51 or the strength ofthe acidity.

Now, if using an exhaust purification catalyst 13 with a strongoxidizing strength, as shown in FIG. 11, if maintaining the air-fuelratio (A/F)in lean while periodically lowering the air-fuel ratio(A/F)in, the hydrocarbons end up becoming completely oxidized when theair-fuel ratio (A/F)in is reduced. As a result, the reducingintermediate can no longer be produced. As opposed to this, when usingan exhaust purification catalyst 13 with a strong oxidizing strength, asshown in FIG. 10, if making the air-fuel ratio (A/F)in periodicallyrich, when the air-fuel ratio (A/F)in is made rich, the hydrocarbonswill be partially oxidized, without being completely oxidized, that is,the hydrocarbons will be reformed, consequently the reducingintermediate will be produced. Therefore, when using an exhaustpurification catalyst 13 with a strong oxidizing strength, the demandedminimum air-fuel ratio X has to be made rich.

On the other hand, when using an exhaust purification catalyst 13 with aweak oxidizing strength, as shown in FIG. 11, if maintaining theair-fuel ratio (A/F)in lean while periodically lowering the air-fuelratio (A/F)in, the hydrocarbons will be partially oxidized without beingcompletely oxidized, that is, the hydrocarbons will be reformed andconsequently the reducing intermediate will be produced. As opposed tothis, when using an exhaust purification catalyst 13 with a weakoxidizing strength, as shown in FIG. 10, if making the air-fuel ratio(A/F)in periodically rich, a large amount of hydrocarbons will beexhausted from the exhaust purification catalyst 13 without beingoxidized and consequently the amount of hydrocarbons which is wastefullyconsumed will increase. Therefore, when using an exhaust purificationcatalyst 13 with a weak oxidizing strength, the demanded minimumair-fuel ratio X has to be made lean.

That is, it is learned that the demanded minimum air-fuel ratio X, asshown in FIG. 12, is reduced the stronger the oxidizing strength of theexhaust purification catalyst 13. In this way the demanded minimumair-fuel ratio X becomes lean or rich due to the oxidizing strength ofthe exhaust purification catalyst 13. Below, taking as example the casewhere the demanded minimum air-fuel ratio X is rich, the amplitude ofthe change in concentration of hydrocarbons flowing into the exhaustpurification catalyst 13 and the vibration period of the concentrationof hydrocarbons flowing into the exhaust purification catalyst 13 willbe explained.

Now, if the base air-fuel ratio (A/F)b becomes larger, that is, if theoxygen concentration in the exhaust gas before the hydrocarbons are fedbecomes higher, the feed amount of hydrocarbons required for making theair-fuel ratio (A/F)in the demanded minimum air-fuel ratio X or lessincreases and along with this the excess amount of hydrocarbons whichdid not contribute the production of the reducing intermediate alsoincreases. In this case, to remove the NO_(x) well, as explained above,it is necessary to make the excess hydrocarbons oxidize. Therefore, toremove the NO_(x) well, the larger the amount of excess hydrocarbons,the larger the amount of oxygen which is required.

In this case, if raising the oxygen concentration in the exhaust gas,the amount of oxygen can be increased. Therefore, to remove the NO_(x)well, when the oxygen concentration in the exhaust gas before thehydrocarbons are fed is high, it is necessary to raise the oxygenconcentration in the exhaust gas after feeding the hydrocarbons. Thatis, the higher the oxygen concentration in the exhaust gas before thehydrocarbons are fed, the larger the amplitude of the hydrocarbonconcentration has to be made.

FIG. 13 shows the relationship between the oxygen concentration in theexhaust gas before the hydrocarbons are fed and the amplitude ΔH of thehydrocarbon concentration when the same NO_(x) purification rate isobtained. To obtain the same NO_(x) purification rate, from FIG. 13, itis learned that the higher the oxygen concentration in the exhaust gasbefore the hydrocarbons are fed, the greater the amplitude ΔH of thehydrocarbon concentration has to be made. That is, to obtain the sameNO_(x) purification rate, the higher the base air-fuel ratio (A/F)b, thegreater the amplitude ΔT of the hydrocarbon concentration has to bemade. In other words, to remove the NO_(x) well, the lower the baseair-fuel ratio (A/F)b, the more the amplitude ΔT of the hydrocarbonconcentration can be reduced.

In this regard, the base air-fuel ratio (A/F)b becomes the lowest at thetime of an acceleration operation. At this time, if the amplitude ΔH ofthe hydrocarbon concentration is about 200 ppm, it is possible to removethe NO_(x) well. The base air-fuel ratio (A/F)b is normally larger thanthe time of acceleration operation. Therefore, as shown in FIG. 14, ifthe amplitude ΔH of the hydrocarbon concentration is 200 ppm or more, anexcellent NO_(x) purification rate can be obtained.

On the other hand, it is learned that when the base air-fuel ratio(A/F)b is the highest, if making the amplitude ΔH of the hydrocarbonconcentration 10000 ppm or so, an excellent NO_(x) purification rate isobtained. Accordingly, in the present invention, the predetermined rangeof the amplitude of the hydrocarbon concentration is made 200 ppm to10000 ppm.

Further, if the vibration period ΔT of the hydrocarbon concentrationbecomes longer, the oxygen concentration around the active NO₂* becomeshigher in the time after the hydrocarbons are fed to when thehydrocarbons are next fed. In this case, if the vibration period ΔT ofthe hydrocarbon concentration becomes longer than about 5 seconds, theactive NO₂* starts to be absorbed in the form of nitrates inside thebasic layer 53. Therefore, as shown in FIG. 15, if the vibration periodΔT of the hydrocarbon concentration becomes longer than about 5 seconds,the NO_(x) purification rate falls. Therefore, the vibration period ΔTof the hydrocarbon concentration has to be made 5 seconds or less.

On the other hand, if the vibration period ΔT of the hydrocarbonconcentration becomes about 0.3 second or less, the fed hydrocarbonsstart to build up on the exhaust gas flow surface of the exhaustpurification catalyst 13, therefore, as shown in FIG. 15, if thevibration period ΔT of the hydrocarbon concentration becomes about 0.3second or less, the NO_(x) purification rate falls. Therefore, in thepresent invention, the vibration period of the hydrocarbon concentrationis made from 0.3 second to 5 seconds.

Next, the NO_(x) purification method when making the exhaustpurification catalyst 13 function as a NO_(X) storage catalyst will bespecifically explained while referring to FIG. 16 to FIG. 20. The NO_(X)purification method when making the exhaust purification catalyst 13function as an NO_(X) storage catalyst in this way will be referred tobelow as the second NO_(X) purification method.

In this second NO_(X) purification method, as shown in FIG. 16, when thestored NO_(X) amount ΣNOX which is stored in the basic layer 53 exceedsa predetermined allowable amount MAX, the air-fuel ratio (A/F)in of theexhaust gas flowing into the exhaust purification catalyst 13 is madetemporarily rich. If the air-fuel ratio (A/F)in of the exhaust gas ismade rich, the NO_(x) which was stored in the basic layer 53 when theair-fuel ratio (A/F)in of the exhaust gas was lean is released all atonce from the basic layer 53 and reduced. Due to this, the NO_(X) isremoved.

The stored NO_(X) amount ΣNOX is, for example, calculated from thestored NO_(X) amount of NO_(x) which is exhausted from the engine andstored in the basic layer 53. In an embodiment of the present invention,the stored NO_(X) amount NOXA of NO_(x) which is exhausted from theengine per unit time and is stored in the basic layer 53 is stored as afunction of the injection amount Q and engine speed N in the form of amap as shown in FIG. 17 in advance in the ROM 32. The stored NO_(X)amount ΣNOX is calculated from this stored NO_(X) amount NOXA. In thiscase, as explained above, the period by which the air-fuel ratio (A/F)inof the exhaust gas is made rich is normally 1 minute or more.

FIG. 18 shows a discharge rate NOXD of the stored NO_(X) which isdischarged from the exhaust purification catalyst 13 when the air-fuelratio (A/F)in of the exhaust gas is lean. As explained above, the NO_(x)which is stored in the form of nitrates is broken down by heat anddischarged if the temperature TC of the exhaust purification catalyst 13rises. At this time, the NO_(X) discharge rate NOXD, that is, the NO_(X)amount NOXD which is discharged per unit time, rapidly rises if thetemperature TC of the exhaust purification catalyst 13 exceeds the about450° C. heat breakdown starting temperature.

In this second NO_(X) purification method, as shown in FIG. 19, byinjecting additional fuel WR in addition to the combustion use fuel Qinto the combustion chambers 2 from the fuel injectors 3, the air-fuelratio (A/F)in of the exhaust gas flowing into the exhaust purificationcatalyst 13 is made rich. Note that, the abscissa of FIG. 19 shows thecrank angle. This additional fuel WR is injected at a timing where it isburned, but does not appear as engine output, that is, slightly beforeATDC90° after compression top dead center. This fuel amount WR is storedas a function of the injection amount Q and engine speed N in the formof a map as shown in FIG. 20 in advance in the ROM 32. Of course, inthis case, it is also possible to make the feed amount of hydrocarbonsfrom the hydrocarbon feed valve 15 increase so as to make the air-fuelratio (A/F)in of the exhaust gas rich.

Now, in the present invention, normally, the first NO_(X) purificationmethod is used. At this time, by changing the hydrocarbon feed amountand injection timing from the hydrocarbon feed valve 15, the amplitudeΔH and vibration period ΔT of the hydrocarbon concentration arecontrolled so as to become optimal values in accordance with theoperating state of the engine. In this case, as explained above, thereducing intermediate performs a central role for the purification ofNO_(X). Therefore, it is believed most suitable to focus on productionof the reducing intermediate and control the amplitude ΔH and vibrationperiod ΔT of the hydrocarbon concentration.

Therefore, in the present invention, as explained above, the amplitudeΔH and vibration period ΔT of the concentration of hydrocarbon flowinginto the exhaust purification catalyst 13 is controlled so as to producea sufficient amount of a reducing intermediate for reducing the NO_(X).Explained in a bit more detail, in the present invention, at the time ofengine operation, the demanded produced amount of the reducingintermediate required for reducing the NO_(X) is calculated, and theamplitude ΔH and vibration period ΔT of the concentration ofhydrocarbons flowing into the exhaust purification catalyst 13 iscontrolled so that the amount of production of the reducing intermediatebecomes this demanded produced amount.

Therefore, first, the demanded produced amount of the reducingintermediate will be explained.

Now, the reducing intermediate R—NCD or R—NH₂ is produced from a singleNO_(X). Therefore, the demanded produced amount of the reducingintermediate (mol) required for reducing the NO_(X) matches with theNO_(X) amount (mol) to be reduced. In this case, the NO_(X) amount to bereduced becomes the sum of the inflowing NO_(X) amount which isexhausted from the engine and flows into the exhaust purificationcatalyst 13 and the released NO_(X) amount which is stored in theexhaust purification catalyst 13 and is released from the exhaustpurification catalyst 13. Therefore, the sum of these inflowing NO_(X)amount and released NO_(X) amount expresses the demanded produced amountof the reducing intermediate. If NO_(x) is not stored in the exhaustpurification catalyst 13, the released NO_(X) amount becomes zero.Therefore, in this case, the inflowing NO_(X) amount expresses thedemanded produced amount of the reducing intermediate.

Note that, if able to maintain the amount of production of the reducingintermediate at the demanded produced amount, it is possible to removeall of the NO_(X) to be reduced. Therefore, in the present invention, asexplained above, the amplitude ΔH and vibration period ΔT of theconcentration of hydrocarbon flowing into the exhaust purificationcatalyst 13 are controlled so that the amount of production of thereducing intermediate becomes the demanded produced amount.

Now, in an embodiment of the present invention, as the demanded producedamount of the reducing intermediate, the demanded produced amount perunit time, that is, the demanded production rate, is used. Similarly, asthe inflowing NO_(X) amount and released NO_(X) amount, the inflowingNO_(X) amount per unit time, that is, the NO_(X) inflow rate, and thereleased NO_(X) amount per unit time, that is, the NO_(X) release rate,are used. In this case, the sum of the NO_(X) inflow rate and the NO_(X)release rate expresses the demanded production rate of the reducingintermediate.

FIGS. 21A and 21B show the relationship between the NO_(X) release rateof release from the exhaust purification catalyst 13 and the temperatureTC of the exhaust purification catalyst 13 and the relationship betweenthe NO_(X) release rate and the amplitude ΔH of the hydrocarbonconcentration when NO_(X) purification processing is performed by thefirst NO purification method in the state where NO_(x) is stored in theexhaust purification catalyst 13. As shown in FIG. 21A, if thetemperature TC of the exhaust purification catalyst 13 becomes higher,the NO_(X) release rate becomes higher.

On the other hand, if the oxygen concentration in the exhaust gasflowing into the exhaust purification catalyst 13 falls, NO_(X) isreleased from the exhaust purification catalyst 13. At this time, thelarger the drop in the oxygen concentration, the greater the amount ofrelease of NO_(X). Therefore, as shown in FIG. 21B, if the amplitude ΔHof the hydrocarbon concentration becomes greater, the NO_(X) releaserate becomes higher. In this regard, if the operating state of theengine is determined, the temperature TC of the exhaust purificationcatalyst 13 and the amplitude ΔH of the hydrocarbon concentration arepretty much determined. Therefore, if the operating state of the engineis determined, the NO_(X) release rate is determined. Therefore, in anembodiment of the present invention, the NO_(X) release rate NOXD perunit time is stored as a function of the injection amount Q of fuel fromthe fuel injector 3 and engine speed N in the form of a map as shown inFIG. 21C in advance in the ROM 32.

In the present invention, the released NO_(X) amount is calculated bymultiplying the stored NO_(X) amount which is stored in the exhaustpurification catalyst 13 with the NO_(X) release rate, that is, from thestored NO_(X) amount and the NO_(X) release rate. In this case, in anembodiment of the present invention, the stored NO_(X) amount isconstantly calculated as the ΣNOX shown in FIG. 16. This stored NO_(X)amount ΣNOX is multiplied with the NO_(X) release rate NOXD to calculatethe NO_(X) release rate (ΣNOX·NOXD). On the other hand, the NO_(X)inflow rate is made the value NOXA of the map shown in FIG. 17.Therefore, the demanded production rate of the reducing intermediate isexpressed by (ΣNOX·NOXD+NOXA). Note that, in this case, it is possibleto multiply (ΣNOX·NOXD+NOXA) with the purification rate demanded for theexhaust purification system according to the present invention so as toobtain the demanded production rate of the reducing intermediate.

Next, referring to FIG. 22A and FIG. 22B, the reducing intermediateholding time able to hold the reducing intermediate produced on thebasic layer 53 of the exhaust purification catalyst 13 will beexplained. If the temperature TC of the exhaust purification catalyst 13rises, the produced reducing intermediate easily separates from thebasic layer 53. Therefore, as shown in FIG. 22A, as the temperature TCof the exhaust purification catalyst 13 becomes higher, the reducingintermediate holding time becomes shorter.

Now, if the vibration period ΔT of the hydrocarbon concentration becomeslonger compared with the reducing intermediate holding time, a timeperiod arises where there is no reducing intermediate and the NO_(X)purification rate ends up falling. To prevent such a time period wherethere is no reducing intermediate from arising, the vibration period ΔTof the hydrocarbon concentration has to be made equal to the reducingintermediate holding time or has to be made shorter than the reducingintermediate holding time. Therefore, the vibration period ΔT of thehydrocarbons, as shown in FIG. 22B, is made shorter as the temperatureTC of the exhaust purification catalyst 13 becomes higher. Therelationship shown in FIG. 22A and FIG. 22B is stored in advance in theROM 32.

Next, referring to FIGS. 23A and 23B, the feed amount of hydrocarbons WFwill be explained. FIG. 23A and FIG. 23B show the relationship betweenthe reducing intermediate production rate K₁ of the time and thetemperature TC of the exhaust purification catalyst 13 and therelationship between the reducing intermediate production rate K₂ andthe injection amount Q from the fuel injector 3 when the reducingintermediate is produced by the fed hydrocarbons.

The reducing intermediate rapidly rises when the exhaust purificationcatalyst 13 is activated. Therefore, as shown in FIG. 23A, the reducingintermediate production rate K₁ rapidly rises when the temperature TC ofthe exhaust purification catalyst 13 becomes higher then graduallyincreases along with the rise of the temperature TC.

On the other hand, if the injection amount Q increases, that is, if theengine load becomes higher, the amount of NO_(x) which is exhausted fromthe engine increases, therefore the demanded feed amount of thehydrocarbons also increases. However, if overly increasing the feedamount of hydrocarbons, the consumed amount of the hydrocarbonsexcessively increases. Therefore, to prevent the amount of consumptionof hydrocarbons from excessively increasing in this way, if theinjection amount Q increases, as shown in FIG. 23B, the reducingintermediate production rate K₂ is lowered. The relationship shown inFIG. 23A and FIG. 23B is stored in advance in the ROM 32.

If multiplying the feed amount of hydrocarbons WF with the two reducingintermediate production rates K₁, K₂, the produced reducing intermediateamount (WF·K₁·K₂) is obtained. In the present invention, this reducingintermediate amount (WF·K₁·K₂) is made the demanded produced amount ofthe reducing intermediate. Therefore, the feed amount of hydrocarbons WFbecomes the demanded produced amount of the reducing intermediatedivided by (K₁·K₂). The feed amount of hydrocarbons WF is calculated inthis way. That is, the amplitude ΔH of the hydrocarbon concentration isdetermined.

That is, in the present invention, the holding time of the reducingintermediate which is held in the exhaust purification catalyst 13 andthe reducing intermediate production rates K₁ and K₂ of the time whenthe reducing intermediate is produced from the fed hydrocarbons arestored in advance. The amplitude and vibration period of theconcentration of hydrocarbons flowing to the exhaust purificationcatalyst 13 are calculated from the demanded produced amount of thereducing intermediate, the holding time of the reducing intermediate,and the reducing intermediate production rates K₁ and K₂.

Note that, in an embodiment of the present invention, as the reducingintermediate production rate K₁ shown in FIG. 23A, the reducingintermediate production rate per unit time is used. Therefore, in thisembodiment, the amount of production of the reducing intermediate untilhydrocarbons are next fed becomes the value of (WF·F₁·F₂) multipliedwith the feed period ΔT of hydrocarbons. Therefore, in this case, thefeed amount of hydrocarbons WF becomes the value of the demandedproduced amount of the reducing intermediate divided by (K₁·K₂·ΔT).

Next, a simple method for finding the feed amount of hydrocarbons WFwill be explained with reference to FIGS. 24A to 25B.

FIG. 24A shows the maximum produced amount M of the possible productionof the reducing intermediate obtained using the reducing intermediateholding time or the reducing intermediate production rate or obtained byexperiments. As will be understood from FIG. 24A, this maximum producedamount. M becomes the relationship of the injection amount Q and enginespeed N from the fuel injector 3. On the other hand, FIG. 24B shows thechange in the maximum produced amount M of the reducing intermediate onthe line MX passing through the origin 0 of FIG. 24A. Note that, in FIG.24A, M_(a1), M_(a2), M_(max), M_(b1), M_(b2), and M_(b3) show the equalmaximum production lines, while M_(max) shows the equivalent maximumproduction line giving the large maximum produced amount M.

As will be understood from FIG. 24A and FIG. 25B, the lower the enginespeed N and the smaller the injection amount Q, the smaller the maximumproduced amount M, while the higher the engine speed N and the greaterthe injection amount Q, the smaller the maximum produced amount M.

Note that, in this embodiment, in actuality, M expresses the maximumproduced amount per unit time, that is, the maximum production rate ofpossible production of the reducing intermediate. The feed amount ofhydrocarbons W and the feed period ΔT of hydrocarbons of the time whenthis maximum production rate M is obtained are stored as function of theinjection amount Q and engine speed N in the form of a map as shown inFIG. 25A and FIG. 25B in advance in the ROM 32.

Therefore, the feed amount of hydrocarbons W shown in FIG. 25A expressesthe maximum feed amount in each operating state. Therefore, the feedamount of hydrocarbons is limited by the maximum feed amount W shown inFIG. 25A. On the other hand, when the demanded produced amount of thereducing intermediate is smaller than the maximum produced amount M, ifmaking the feed amount of hydrocarbons smaller than the maximum feedamount W shown in FIG. 25A, the amount of production of the reducingintermediate can be made the demanded produced amount.

At this time, in this embodiment, the feed amount of hydrocarbons ismade the value obtained by multiplying the maximum feed amount W, whichis determined in accordance with the operating state of the engine andshown in FIG. 25A, with the (demanded production rate of reducingintermediate/maximum production rate M of reducing intermediate), whilethe feed period of the hydrocarbons is made the period ΔT in accordancewith the operating state of the engine shown in FIG. 25B. In this way,in this embodiment, the maximum produced amount M of possible productionof the reducing intermediate is stored in advance, and the amplitude ΔHand vibration period ΔT of the concentration of hydrocarbons flowinginto the exhaust purification catalyst 13 are calculated from themaximum produced amount M and the demanded produced amount of thereducing intermediate.

Next, NO_(x) release control according to the present invention will beexplained.

FIG. 26 shows an NO_(X) purification rate of the time when the firstNO_(X) purification method is used for NO_(X) purification processingand the NO_(X) storage rate to the exhaust purification catalyst 13 atthe time when the second NO_(X) purification method is used. In thepresent invention, when the NO_(X) purification rate is higher than theNO_(X) storage rate, that is, when the temperature TC of the exhaustpurification catalyst 13 is relatively high, the first NO_(X)purification method is used. When the NO_(X) storage rate is higher thanthe NO_(X) purification rate, that is, when the temperature TC of theexhaust purification catalyst 13 is low, the second NO_(X) purificationmethod is used. Therefore, at the time of engine startup, usually thesecond NO_(X) purification method is used. When the temperature TC ofthe exhaust purification catalyst 13 becomes high, the second NO_(X)purification method is switched to the first NO_(X) purification method.

On the other hand, when the first NO_(X) purification method is used toperform the NO_(X) purification processing, if the NO_(X) amount to beremoved rapidly increases, sometimes the amount of reducing intermediaterequired for reducing the increased NO_(X) can no longer be produced. Inan embodiment of the present invention, the maximum produced amount M ofpossible production of the reducing intermediate shown in FIG. 24A isstored in the ROM 32 in advance. When the demanded produced amount ofthe reducing intermediate exceeds the maximum produced amount M, it isjudged that the amount of reducing intermediate required for reducingthe NO_(X) can no longer be produced.

In this regard, if the amount of reducing intermediate required forreducing the NO_(X) can no longer be produced in this way, that is, ifthe demanded produced amount of the reducing intermediate becomes largerthan the maximum produced amount M shown in FIG. 24A, unless some sortof step is taken, a large amount of NO_(X) will end up being exhaustedfrom the exhaust purification catalyst 13. In the typical case where thedemanded produced amount of the reducing intermediate becomes largerthan the maximum produced amount M shown in FIG. 24A, the second NO_(X)purification method is switched to the first purification method in thestate where a large amount of NO_(X) is stored in the exhaustpurification catalyst 13.

At this time, the NO_(X) which is stored in the exhaust purificationcatalyst 13 is rapidly released, so the demanded produced amount of thereducing intermediate becomes larger than the maximum produced amount Mshown in FIG. 24A. At this time, in one embodiment according to thepresent invention, the feed amount of hydrocarbons is increased toincrease the amount of hydrocarbons which is used for reduction of theNO_(X), whereby the air-fuel ratio of the exhaust gas flowing into theexhaust purification catalyst 13 is temporarily made rich. FIG. 27 showsthe time chart at this time, that is, at the time when the second NO_(X)purification method is switched to the first NO_(X) purification method.

Note that, FIG. 27 shows an injection timing of the additional fuel WR,a feed timing of hydrocarbons WR, a change of the air-fuel ratio (A/F)inof the exhaust gas flowing into the exhaust purification catalyst 13,and a change of the stored NO_(X) amount ΣNOX stored in the exhaustpurification catalyst 13. As shown in FIG. 27, when the second NO_(X)purification method is switched to the first NO_(X) purification methodwhen the stored NO_(X) amount ΣNOX is a positive value, NO_(x) isreleased from the exhaust purification catalyst 13. To reduce the NO_(x)which is released at this time, the additional fuel WR is fed and theinflowing air-fuel ratio (A/F)in is temporarily made rich. After that,the NO_(X) purification processing by the first NO_(X) purificationmethod is started.

FIG. 28 shows a control routine for NO_(x) purification for working thisembodiment. This routine is executed by interruption every predeterminedtime interval.

Referring to FIG. 28, first, at step 60, it is judged if the NO_(x)storage rate to the exhaust purification catalyst 13 where the secondNO_(X) purification method is used is lower than the NO_(x) purificationrate when using the first NO_(X) purification method to perform theNO_(X) purification processing. When the NO_(X) storage rate is higherthan the NO_(X) purification rate, the routine proceeds to step 61 wherethe second NO_(X) purification method is performed.

That is, at step 61, the stored NO_(X) amount NOXA per unit time iscalculated from the map shown in FIG. 17, while the NO_(X) dischargerate NOXB is calculated from the relationship shown in FIG. 18. Next, atstep 62, the following formula is used as the basis to calculate theNO_(X) amount ΣNOX which is stored in the exhaust purification catalyst14 during the NO_(X) purification action by the first NO_(X)purification method.ΣNOX←ΣNOX+NOXA−NOXD

Next, at step 63, it is judged if the stored NO_(X) amount ΣNOX exceedsthe allowable value MAX. If ΣNOX>MAX, the routine proceeds to step 64where the additional fuel amount WR is calculated from the map shown inFIG. 20 and the injection action of additional fuel is performed. Next,at step 65, ΣNOX is cleared.

On the other hand, when it is judged at step 60 that the NO_(X) storagerate is lower than the NO_(X) purification rate, the routine proceeds tostep 66 where the stored NO_(x) amount per unit time, that is, theNO_(x) inflow rate NOXA, is calculated from the map shown in FIG. 17 andthe NO_(X) release rate NOXD per unit time is calculated from the mapshown in FIG. 21C. Next, at step 67, the maximum production rate M ofthe reducing intermediate is calculated from the relationship shown inFIG. 24A. Next at step 68, the sum NX of the NO_(X) inflow rate NOXA andthe NO_(X) release rate (NOXD·ΣNOX) is calculated. Next, at step 69, itis judged if this sum NX is larger than the maximum production rate M ofthe reducing intermediate.

When the sum NX is smaller than the maximum production rate M, theroutine proceeds to step 70 where the first NO_(X) purification methodis used to perform NO_(X) purification processing. That is, at step 70,the demanded production rate of the reducing intermediate RM iscalculated. In this embodiment, the sum NX is made the demandedproduction rate RM. In this case, this sum NX can be multiplied with thepurification rate demanded for the exhaust purification system accordingto the present invention to obtain the demanded production rate RM. Inthis case, RM<NX.

Next, at step 71, the maximum feed amount W of hydrocarbons calculatedfrom the map shown in FIG. 25A is multiplied with (demanded productionrate RM/maximum production rate M) so as to calculate the feed amount ofhydrocarbons WF (=(RM/M)·W). Next, at step 72, the feed period ΔT ofhydrocarbons is calculated from the map shown in FIG. 25B. Next, at step73, the calculated feed amount WF and feed period ΔT are used for feedcontrol of the hydrocarbons.

On the other hand, when it is judged at step 69 that the sum NX of theNO_(X) inflow rate and NO_(X) release rate is larger than the maximumproduction rate M of the reducing intermediate, the routine proceeds tostep 74 where the additional fuel amount required for reduction of thestored NO_(X) is calculated and the injection action of additional fuelis performed. Next, at step 75, ΣNOX is cleared.

FIG. 29A to FIG. 32 show another embodiment. In this embodiment, whenthe amount of reducing intermediate required for reducing the NO_(X)cannot be produced, to increase the amount of hydrocarbons used forproduction of the reducing intermediate, the base air-fuel ratio (A/F)bis made smaller without changing the amplitude ΔH of the hydrocarbonconcentration. That is, the state shown in FIG. 29A is made the stateshown in FIG. 29B.

If the base air-fuel ratio (A/F)b is made smaller without changing theamplitude ΔH of the hydrocarbon concentration in this way, the minimumair-fuel ratio of the time when the hydrocarbons are fed becomesconsiderably small. As a result, the amount of hydrocarbons used forproducing the reducing intermediate is increased. As a result, theamount of production of the reducing intermediate is increased and alarge amount of NO_(X) can be processed.

In an embodiment of the present invention, the base air-fuel ratio(A/F)b is made smaller by making the opening degree of the throttlevalve 10 smaller compared with the time of usual operation shown in FIG.29A. In this embodiment, the opening degree θA of the throttle valve 10at the time of normal operation shown in FIG. 29A and the opening degreeθB of the throttle valve 10 at the time of when the base air-fuel ratio(A/F)b is made smaller as shown in FIG. 29B are found in advance. Theseopening degrees θA and θB are stored as a function of the injectionamount Q and engine speed N in the form of a map in advance in the ROM32. FIG. 30 shows a map of the opening degree θB stored in the ROM 32.

In this embodiment, as shown in FIG. 31, when the second NO_(X)purification method is switched to the first NO_(X) purification method,right after switching, the base air-fuel ratio (A/F)b is temporarilymade smaller.

FIG. 32 shows the control routine for NO_(x) purification for workingthis embodiment. This routine is also executed by interruption everypredetermined time interval. Note that, steps 80 to 89 in this routineare the same as steps 60 to 69 of the routine shown in FIG. 28. Further,steps 92 to 95 of the routine shown in FIG. 32 are the same as steps 70to 73 of the routine shown in FIG. 28.

That is, referring to FIG. 32, first, at step 80, it is judged if theNO_(x) storage rate to the exhaust purification catalyst 13 at the timewhen the second NO_(x) purification method is used is lower than theNO_(x) purification rate at the time the first NO_(X) purificationmethod is used to perform the NO_(X) purification processing. When theNO_(X) storage rate is higher than the NO_(X) purification rate, theroutine proceeds to step 81 where the second NO_(X) purification methodis performed.

That is, at step 81, the stored NO_(X) amount NOXA per unit time iscalculated from the map shown in FIG. 17, while the NO_(X) dischargerate NOXB is calculated from the relationship shown in FIG. 18. Next, atstep 82, the following formula is used as the basis to calculate theNO_(X) amount ΣNOX stored in the exhaust purification catalyst 14 duringthe NO_(x) purification action by the first NO_(X) purification method.ΣNOX←ΣNOX+NOXA−NOXD

Next, at step 83, it is judged if the stored NO_(X) amount ΣNOX exceedsthe allowable value MAX. When ΣNOX>MAX, the routine proceeds to step 84where the additional fuel amount WR is calculated from the map shown inFIG. 20 and an injection action of additional fuel is performed. Next,at step 85, ΣNOX is cleared.

On the other hand, when it is judged at step 80 that the NO_(X) storagerate is lower than the NO_(X) purification rate, the routine proceeds tostep 86 where the stored NO_(x) amount per unit time, that is, theNO_(x) inflow rate NOXA, is calculated from the map shown in FIG. 17,and the NO_(X) release rate NOXD per unit time is calculated from themap shown in FIG. 21C. Next, at step 87, the maximum production rate Mof the reducing intermediate is calculated from the relationship shownin FIG. 24A. Next, at step 88, the sum NX of the NO_(X) inflow rate NOXAand the NO_(X) release rate (NOXD·ΣNOX) is calculated. Next, at step 89,it is judged if this sum NX is larger than the maximum production rate Mof the reducing intermediate.

When the sum NX is smaller than the maximum production rate M, theroutine proceeds to step 90 where the usual NO_(X) purificationprocessing by the first NO_(X) purification method is performed. Thatis, at step 90, the stored opening degree θA of the throttle valve 10 atthe time of normal operation is calculated, then the opening degree ofthe throttle valve 10 is made the opening degree θA. Next, at step 90,the demanded production rate of the reducing intermediate RM iscalculated. In this embodiment, the sum NX is made the demandedproduction rate RM. In this case, as explained above, this sum NX can bemultiplied with the production rate found for the exhaust purificationsystem according to the present invention to obtain the demandedproduction rate RM.

Next, at step 93, the maximum feed amount W of the hydrocarbonscalculated from the map shown in FIG. 25A is multiplied with the(demanded production rate RM/maximum production rate M) to calculate thefeed amount of hydrocarbons WF(=(RM/M)·W). Next, at step 94, the feedperiod ΔT of hydrocarbons is calculated from the map shown in FIG. 25B.Next, at step 95, the calculated feed amount WF and feed period ΔT areused for feed control of the hydrocarbons.

On the other hand, when it is judged at step 89 that the sum NX of theNO_(X) inflow rate and the NO_(X) release rate is larger than themaximum production rate M of the reducing intermediate, the routineproceeds to step 91 where the opening degree θB of the throttle valve 10for making the base air-fuel ratio (A/F)b smaller is calculated from themap shown in the FIG. 30 and the opening degree of the throttle valve 10is made this opening degree θB. Next, the routine proceeds to step 92.

In this way, in the embodiment shown in FIG. 27 to FIG. 31, when theamount of reducing intermediate required for reducing the NO_(X) cannotbe produced, the amount of hydrocarbons which is used for producing thereducing intermediate or reducing the NO_(X) is temporarily increased.

Next, referring to FIG. 33, still another embodiment will be explained.FIG. 33 shows the case where additional fuel WR is fed to the combustionchamber 2 so as to make the air-fuel ratio of the exhaust gas of theexhaust purification catalyst 13 temporarily rich to make the exhaustpurification catalyst 13 release the stored NO_(X) when the secondNO_(X) purification method is being used. Note that, in FIG. 33, TXshows the activation temperature of the exhaust purification catalyst13. Therefore, FIG. 33 shows case when the temperature TC of the exhaustpurification catalyst 13 is less than the activation temperature TXbefore the additional fuel WR is fed, that is, before rich control isperformed for making the inflowing air-fuel ratio (A/F)in rich.

As shown in FIG. 33, if rich control is started, the heat of theoxidation reaction of the hydrocarbons which are exhausted from thecombustion chamber 2 causes the temperature TC of the exhaustpurification catalyst 13 to rapidly rise and exceed the activationtemperature TX. On the other hand, even if rich control is started, thehydrocarbons which are exhausted from the combustion chambers 2 are usedto consume the oxygen stored inside the exhaust purification catalyst13. Therefore, even if rich control is started, the inflowing air-fuelratio (A/F)b of the exhaust gas which flows into the exhaustpurification catalyst 13 will not immediately become rich.

Now, if rich control is started and the inflowing air-fuel ratio (A/F)inbecomes smaller, the NO_(x) stored in the exhaust purification catalyst13 is rapidly released. At this time, as shown in FIG. 33 at t₁, thereis a time period where the temperature TC of the exhaust purificationcatalyst 13 becomes the activation temperature TX or more and theinflowing air-fuel ratio (A/F)in becomes lean. In this time period t₁,if the first NO_(X) purification method is used for the NO_(X)purification processing, the released NO_(X) is used to produce thereducing intermediate and this reducing intermediate is used to reducethe released NO_(X). Therefore, in this embodiment, in the time periodt₁ of possible production of this reducing intermediate, thehydrocarbons WF are fed and the first NO_(x), purification method isused for NO_(X) purification processing.

On the other hand, even after completion of rich control, as shown inFIG. 33 at t₂, there is a time period where the temperature TC of theexhaust purification catalyst 13 becomes an activation temperature TX ormore and the inflowing air-fuel ratio (A/F)in becomes lean. In this timeperiod t₂ as well, if using the first NO_(X) purification method toperform NO_(X) purification processing, the released NO_(X) is used toproduce the reducing intermediate. In this case as well, this reducingintermediate is used to reduce the released NO_(X). However, in thiscase, to build up the produced reducing intermediate, the hydrocarbonsWF are fed by the time period t₂ of possible production of this reducingintermediate.

That is, in this embodiment, hydrocarbons WF are fed so as to be able toproduce a reducing intermediate at the exhaust purification catalyst 13at a possible reducing intermediate production period t₁ before theair-fuel ratio (A/F)in of the exhaust gas flowing to the exhaustpurification catalyst 13 is switched from lean to rich after theadditional fuel WR is fed and at the possible reducing intermediateproduction period t₂ after the air-fuel ratio (A/F)in of the exhaust gasflowing into the exhaust purification catalyst 13 is switched from richto lean.

On the other hand, if the exhaust purification catalyst 13 deterioratesdue to heat or is poisoned by sulfur, the NO_(X) storage ability and theholding ability of the reducing intermediate fall. Therefore, in thiscase, the storable amount of NO_(x) and the reducing intermediateholding time shown in FIG. 22A are preferably corrected in accordancewith the heat deterioration or sulfur poisoning of the exhaustpurification catalyst 13. FIG. 34A shows the correction coefficient forthe storable amount of NO_(X), while FIG. 34B shows the correctioncoefficient for the reducing intermediate holding time.

As shown in FIG. 34A, the correction coefficient for the storable amountof the NO_(X) is made smaller the longer the driving distance of thevehicle, that is, the greater the heat deterioration of the exhaustpurification catalyst 13 or sulfur poisoning amount. In this case, forexample, if multiplying the allowable value MAX shown in FIG. 16 withthis correction coefficient, the period of the rich control at the timewhen the second NO_(X) purification method is used is made shorter thelonger the driving distance of the vehicle. On the other hand, as shownin FIG. 34B, the correction coefficient for the reducing intermediateholding time is made smaller the greater the sulfur poisoning amount. Inthis case, for example, if multiplying the ΔT shown in FIG. 22B withthis correction coefficient, the feed period ΔT of hydrocarbons is madeshorter the greater the sulfur poisoning amount.

Note that, as another embodiment, it is also possible to arrange anoxidation catalyst for reforming the hydrocarbons in the engine exhaustpassage upstream of the exhaust purification catalyst 13 and possible toarrange a catalyst for storing or holding the NO_(x) in the engineexhaust passage upstream of the exhaust purification catalyst 13. Whenarranging a catalyst storing or holding the NO_(X) in this range, NO_(x)purification control is performed considering also the action of releaseof NO_(x) from this catalyst.

REFERENCE SIGNS LIST

-   4 . . . intake manifold-   5 . . . exhaust manifold-   7 . . . exhaust turbocharger-   12 . . . exhaust pipe-   13 . . . exhaust purification catalyst-   14 . . . particulate filter-   15 . . . hydrocarbon feed valve

The invention claimed is:
 1. A method for purifying exhaust gas of aninternal combustion engine, the method comprising: flowing an exhaustgas containing NO_(x) and a concentration of hydrocarbons in an exhaustgas passage that contains an exhaust purification catalyst, wherein theconcentration of hydrocarbons is vibrated within a predetermined rangeof amplitude and within a predetermined range of period, and a least aportion of the hydrocarbons are reformed by the exhaust purificationcatalyst; reacting the NO_(x) contained in the exhaust gas and thereformed hydrocarbons to produce a reducing intermediate containingnitrogen and hydrocarbons; and chemically reducing the NO_(x) containedin the exhaust gas by a reducing action of the produced reducingintermediate, wherein at the time of engine operation, a demandedproduced amount of the reducing intermediate required for chemicallyreducing the NO_(x) is calculated, and the amplitude and vibrationperiod of the concentration of hydrocarbons flowing into the exhaustpurification catalyst are controlled so that an amount of the reducingintermediate produced becomes the demanded produced amount, wherein whenan electronic control unit controls the vibration of the concentrationof hydrocarbons flowing into the exhaust purification catalyst withinthe predetermined range of amplitude and within the predetermined rangeof period, the exhaust purification catalyst has a property ofchemically reducing the NO_(x) that is contained in the exhaust gaswithout storing, or with storing a fine amount of nitrates in a basiclayer of the exhaust purification catalyst, and wherein the methodfurther comprises a second method, wherein the second method comprisesvibrating the concentration of hydrocarbons longer than thepredetermined range, and when the concentration of hydrocarbons isvibrated longer than the predetermined range, the exhaust purificationcatalyst has a property of being increased in a storage amount ofNO_(x).
 2. The method of claim 1, wherein the demanded produced amountof the reducing intermediate is expressed as a sum of an inflowingNO_(X) amount that is exhausted from an engine and that flows into theexhaust purification catalyst, and a released amount of NO_(X) that isstored in the exhaust purification catalyst and that is released fromthe exhaust purification catalyst.
 3. The method of claim 2, wherein aNO_(x) release rate of NO that is stored in the exhaust purificationcatalyst and that is released from the exhaust purification catalyst isstored in advance, and wherein the released NO_(X) amount is calculatedfrom a stored NO_(X) amount that is stored in the exhaust purificationcatalyst and the NO_(X) release rate.
 4. The method of claim 1, whereinthe method further comprises holding the reducing intermediate in theexhaust purification catalyst, a holding time of the reducingintermediate that is held in the exhaust purification catalyst and areducing intermediate production rate at the time when the reducingintermediate is produced are stored in advance, and the amplitude andvibration period of the concentration of hydrocarbons flowing into theexhaust purification catalyst are calculated from the demandedproduction amount of the reducing intermediate, the holding time of thereducing intermediate, and the reducing intermediate production rate. 5.The method of claim 1, wherein a maximum produced amount of possibleproduction of the reducing intermediate is stored in advance, andwherein the amplitude and vibration period of the concentration ofhydrocarbons flowing into the exhaust purification catalyst arecalculated from the maximum produced amount and the demanded producedamount of the reducing intermediate.
 6. The method of claim 1, whereinthe vibration period of the concentration of hydrocarbons is from 0.3seconds to 5 seconds.
 7. The method of claim 1, wherein when the amountof reducing intermediate required for chemically reducing the NO_(X)cannot be produced, an amount of hydrocarbons used for producing thereducing intermediate or for chemically reducing the NO_(X) istemporarily increased.
 8. The method of claim 7, wherein a maximumproduced amount of possible production of the reducing intermediate isstored in advance, and wherein when the demanded produced amount of thereducing intermediate exceeds the maximum produced amount, an electroniccontrol unit determines that an amount of reducing intermediate requiredfor chemically reducing the NO_(X) cannot be produced.
 9. The method ofclaim 7, wherein when the amount of reducing intermediate required forchemically reducing the NO_(X) cannot be produced, a feed amount ofhydrocarbons is increased to increase the amount of hydrocarbons usedfor reducing the NO_(X) and an air-fuel ratio of an exhaust gas flowinginto the exhaust purification catalyst is temporarily made rich.
 10. Themethod of claim 7, wherein when the amount of reducing intermediaterequired for chemically reducing the NO_(X) cannot be produced, a baseair-fuel ratio is made smaller to increase an amount of hydrocarbonsused for producing the reducing intermediate.
 11. The method of claim 1,wherein the exhaust purification catalyst comprises a precious metalcatalyst comprised of platinum (Pt) and at least one of rhodium (Rh) orpalladium (Pd).
 12. The method of claim 1, wherein the exhaustpurification catalyst comprises a basic layer containing an alkalimetal, an alkali earth metal, a rare earth, or a metal that can donateelectrons to NO_(x).
 13. The method of claim 12, wherein the formedreducing intermediate is held on the basic layer.
 14. The method ofclaim 1, wherein the method further comprises: feeding additional fuelto a combustion chamber so as to make an air-fuel ratio of an exhaustgas flowing into the exhaust purification catalyst temporarily rich torelease a stored amount of NO_(X), and when feeding the additional fuelto a combustion chamber so as to make an air-fuel ratio of an exhaustgas flowing into the exhaust purification catalyst temporarily,hydrocarbons are fed to enable production of the reducing intermediateat the exhaust purification catalyst at a reducing intermediateproduction period before the air-fuel ratio of the exhaust gas flowingto the exhaust purification catalyst is switched from lean to rich afterthe additional fuel is fed, and at a reducing intermediate productionperiod after the air-fuel ratio of the exhaust gas flowing into theexhaust purification catalyst is switched from rich to lean.
 15. Amethod for removing NO_(x) contained in an exhaust gas of an internalcombustion engine, the method comprising: flowing the exhaust gascontaining NO_(x) in an exhaust gas passage that comprises an exhaustpurification catalyst, wherein the exhaust purification catalystoxidizes at least a portion of the NO_(x) in the exhaust gas therebyforming an active NO_(x) compound; increasing a concentration ofhydrocarbons in the exhaust gas, wherein at least a portion of thehydrocarbons are reformed in the exhaust gas catalyst; reacting thereformed hydrocarbons and at least a portion of the active NO_(x)compound to produce a reducing intermediate containing nitrogen andhydrocarbons; lowering the concentration of hydrocarbons in the exhaustgas; and reacting the reducing intermediate and the active NO_(x)compound, thereby chemically removing the NO_(x) contained in an exhaustgas, wherein during the method, the NO_(x) is chemically removed fromthe exhaust gas without storing, or with storing a fine amount ofnitrates in the exhaust purification catalyst, and wherein the methodfurther comprises a second method, wherein the second method comprisesvibrating the concentration of hydrocarbons longer than thepredetermined range, and when the concentration of hydrocarbons isvibrated longer than the predetermined range, the exhaust purificationcatalyst has a property of being increased in a storage amount ofNO_(x).